Process for breaking petroleum emulsions employing oxyalkylation derivatives of certain polyepoxide modified phenol-aldehyde resins



2,792,352 Patented May 14, 195'? polyepoxides employed are characterizedby being essentially hydrophile in character instead of hydrophobe incharacter. As noted in the aforementioned copending application, SerialNumber 324,814, filed December 8, TIVES F CERTAIN POLYEPOE MODIFID 51952, the polyepoxides invariably contain two or more PHENGLALDEHYDERESINS phenolic nuclei but in any event have at least 6 and usually morecarbon atoms in uninterrupted group or Melvin De Gimme: Univfil'silyCity, and I 3 chain and thus contribute essential hydrophobe propergfigfg gfi 3g g gfi gs z g g gz gg ties. Indeed, the invention of ourc-opending application,

g rp 10 Serial Number 324,814 may be characterized by the use NoDrawing. Application February 19, 1953, of diglycidyl compoundsdescribed in said copending ap- Serial No. 337,884 plication and alsoelsewhere. As for example, in U. S.

Claims. (CL z52 331 2,500,449, dated March 14, 1950, to Bradley, inwhich there are described glycidyl ethers represented by the Thisinvention relates to processes or procedures par- 15 formula ticularlyadapted for proventing, breaking, or resolving emulsions of thewater-in-oil type, and particularly a dihydric phenol and n is aninteger of the series 0, 1,

petroleum emulsions. 2, 3, etc. More specifically, such diglycidylethers may Our invention provides an economical and rapid procbeillustrated by the following formula wherein R represents the divalenthydrocarbon radical of ess for resolving petroleum emulsions of thewater-in-oil type, that are commonly referred to as cut oil, roily Incontradistinction to such diglycidyl ethers which oil, emulsified oil,etc., and which comprise fine dropintroduce an essentially hydrophoberadical or radicals, lets of naturally-occurring waters or brinesdispersed the present invention is characterized by analogous comin amore or less permanent state throughout the oil pounds derived fromdiglycidyl ethers which do not introwhich constitutes the continuousphase of the emulsion. duce any hydrophobe properties in its usualmeaning but It also provides an economical and rapid process for in factare more apt to introduce hydrophile properties. separating emulsionswhich have been prepared under Thus, the diepoxides employed in thepresent invention controlled conditions from mineral oil, such as crudeoil are characterized by the fact that the divalent radical conandrelatively soft waters or weak brines. Controlled necting the terminalepoxide radicals contains less than 5 emulsification and subsequentdemulsification under the carbon atoms in an interrupted chain. Forinstance, 21 conditions just mentioned are of significant value inresimple member and one of the most readily available moving impurities,particularly inorganic salts, from pipemembers of the class ofdiepoxides described in our line oil. aforementioned copendingapplication, Serial Number Attention is directed to our copendingapplication 324,814, filed December 8, 1952, is Serial Number 324,814,filed December 8, 1952. Said copending application relates to a processforbreaking petroleum emulsions of the water-in-oil type character- O LQJ3J E 'ized by subjecting the emulsions to the action of a de- H Hmulsifier including synthetic hydrophile products; said 0 L synthetichydrophile products being oxyalkylation deriva- It is to be noted inthis formula the terminal epoxy g i figs g gggg gg g ggi f fifizfi 222333222;: radicals are separated by the divalent hydrophobe group whereinn is an integer of the series 0, 1, 2, 3, etc.

polyepoxides, also therein described in detail. 0f par- CH3 ticularimportance in the process of said c-o-pending ap- H H plication are theoxyalkylation derivatives of the reaction *g* --f products ofphenol-aldehyde resins derived from difunc- L tional monohydric phenolsand aldehyde's having not over 8 carbon atoms, particularly,formaldehyde, in which the The diepoxides employed in the presentprocess are difunctional monohydric phenol residue is derived fromobtained from glycols such as ethylene glycol, diethylene a hydrocarbonsubstituted phenol, with phenolic diy p py y p py y tripropyleneepoxides of the following formula: glycol, butylene glycol, dibutyleneglycol, tributylene glycol, glycerol, diglycerol, triglycerol, andsimilar comnio-on-oHr-0-' C(CH:); pounds. Such products are well knownand are characterized by the fact that there are not more than 4uninterrupted carbon atoms in any group which is part and coglleficallyassooiated compounds formed in their of the radical joining the epoxidegroups. Of necessity p p such diepoxides must be nonaryl or aliphatic inchar- The present invention is analogous to the invention of t Thdigylcidyl th of cgpending li i said aforementioned copendingapplication, Serial Num- Serial Number 324,814, filed December 8, 1952,are inber 324,814, filed December 8, 1952, except that the variably andinevitably aryl in character.

2,792,352 7 a a N The diepoxides employed in the present process are iusually obtained by reacting a glycol or equivalent compound such asglycerol or diglycerol with epichlorohydrin and subsequently with analkali. Such diepoxides have been described in the literature andparticularly the patent literature. See for example, Italian Patent400,97 3, dated August 8, 1941. See also British Patent $518,057 datedDecember 10, 1938. See U. '8. Patent 2,070,990, dated February 16, 1937,to .Groll et a1. Reference is also made to U. S. Patent 2,581,464, datedJanuary 8, 1952, to Zech. This particular last mentioned patentdescribes a composition of the following general .formula in which x isat least 1, z varies from less than 1 to more than 1,, andx and ztogether are at least 2 and not more than 6, and R is the residue of the.polyhydric alcohol remaining after r placement or. at least 2 of thehydroxyl groups thereof with the epoxide ether groups of the aboveformula and any remaining groups of the residue being free hydroxylgroups.

It is obviou from What is said in the patent that variance can beobtained in which the halogen is replaced by a hydroxyl radical, thusthe formula would become Reference to being thermoplastic characterizesthem as being liquids at ordinary temperature or readily convertible toliquids by merely heating below the point of pyrolysis and thusdifferentiates them from infusible resins. Reference to being soluble inan organic solvent means any of the usual organic solvents such asalcohols, ketones, esters, others, mixed solvents, etc. Reference tosolubility is merely to differentiate from a reactant which is notsoluble and might be not only insoluble but also infusible. Furthermore,solubility is a factor insofar that it sometimes is desirable to dilutethe compound containing the epoxy rings before reacting with an aminecondensate. In such instances, of course, the solvent selected wouldhave to be one which is not susceptible to oxyalkylation, as, forexample, kerosene, benzene,

toluene, dioxane, possibly various ketones, chlorinated a 4 omegaposition. This is a departure, of course, from the standpoint ofstrictly formal nomenclature as in the example of the simplest diepoxidewhich contains at least 4 carbon atoms and is formally described as1,2-epoxy- 3,4-epoxybutane (1,2,3,4 diepoxybutane).

'It Well may be that even though the previously suggested formularepresents the principal component, or components, of the resultant orreaction product described in the previous text, it may be important tonote :that somewhat similar compounds, generally of much highermolecular weight, have been described as complex resinous epoxideswhichare polyether derivatives of polyhydric compounds containing anaverage of more than one epoxide group per molecule and free fromfunctional groups other than epoxide and hydroxyl groups. The compoundshere included are limited to the monomers or the low molal members ofsuch series and generally contain two epoxide rings per molecule and maybe entirely free from a hydroxyl group. This is important because theinstant invention is directed towards products which are not insolubleresins and have certain solubility characteristics not inherent in theusual thermosetting resins. Note, for example, that said U. S. PatentNo. 2,494,295 describes products wherein the epoxide derivativeqaCombine with a sulfonarnide resin. The intention in said fS. la'tent2,494,295, of course, is to obtain ultimately a suitable resinousproduct having the characteristics of a comparatively insoluble resin.Simply for purpose of illustration to show a typical diglycidyl ether ofthe kind herein employed, reference is made to the following formula: V

or if derived from cyclic diglycerol the structure would be thus:

Commercially available compounds seem to be largely the former withcomparatively small amounts, in fact comparatively minor amounts, of thelatter.

Having obtained a reactant having generally 2 epoxy ringsas depicted inthe next to last formula preceding, orlow molal polymers thereof, itbecomes obvious the reaction can take place with any phenol-aldehyderesin by virtue of the fact that there are always present reactivehydroxyl radicals which are part of the phenolic nuclei.

To illustrate the "products which represent the subject matter of -thepresent invention reference will be made to a reaction involving a moleof the oxyalkylating agent, i. e., the compound having two oxirane ringsand a phenolaldehyde resin. Proceeding with the example previouslydescribed it is obvious the reactionratio of two moles of thephenol-aldehyde resin to one mole of the oxyalkylating agent gives aproduct which may be indicated as follows:

in which n' is a small whole number less than 10, and usually less than4, and including 0, and R1 represents a divalent radical as previouslydescribed being free from any radical having more than 4 uninterruptedcarbon atoms in a single chain, and the characterization resin is simplyan abbreviation for the resin which is described in greater detailsubsequently.

In recapitulation then the present invention relates to a process forbreaking petroleum emulsions of the waterin-oil type characterized bysubjecting the emulsions to the action of a demulsifier includingsynthetic hydrophile products; said products being oxyalkylationderivatives of the reaction products of certain phenol-aldehyde resins,hereinafter described in detail, with certain non-aryl hydrophilepolyepoxides, also hereinafter described in detail. Of particularimportance are the oxyalkylation derivatives of the reaction products ofphenol-aldehyde resins derived from difunctional monohydric phenols andaldehydes not having over 8 carbon atoms, particularly, formaldehyde, inwhich the difunctional monohydric phenol residue is derived from ahydrocarbon substituted phenol, with nonaryl hydrophile polyepoxidescharacterized by the fact that the percursory polyhydric alcohol, inwhich an oxygenlinked hydrogen atom if subsequently replaced by theradical in the epoxide, is water soluble.

As far as the use of the herein described products goes for the purposeof resolving petroleum emulsions of the water-in-oil type, we prefer toemploy oxyalkylated derivatives, which are obtained by the use ofmono-epoxides, in such manner that the derivatives so obtained havesufficient hydrophile character to meet at least the test set forth inU. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote andKeiser. In said patent such test for emulsification using awater-insoluble solvent, generally xylene, is described as an index ofsurface activity.

In the present instance the various oxyalkylated derivatives obtainedparticularly by use of ethylene oxide, propylene oxide, etc., may notnecessarily be xylenesoluble although they are xylene-soluble in a largenumber of instances. If such compounds are not xylenesoluble the obviouschemical equivalent, or equivalent chemical test, can be made by simplyusing some suitable solvent, preferably a water-soluble solvent such asethylene glycol diethylether, or a low molal alcohol, or a mixture todissolve the appropriate product being examined and then mix with theequal weight of xylene, followed by addition of water. Such testobviously is the same for the reason that there will be two phases onvigorous shaking and surface activity makes its presence manifest. It isunderstood the reference in the hereto appended claims as to the use ofxylene in the emulsification test includes such obvious variant.

Another peculiarity of the compounds herein described is that they maypass into a comparatively high molecular weight range and be effectivefor various purposes, not only for the resolution of petroleum emulsionsbut also for other industrial uses described in detail elsewhere. Thischaracteristic may be related to the fact that the initial resinmolecule, obtained in turn from two resin molecules combined by means ofa polyepoxide as described, results in a fairly large molecule. We havefound we can obtain compounds effective for purposes wheresurface-active materials are employed, whether it be the resolution ofpetroleum emulsions or other uses, in which one part of the derivativeobtained by the polyepoxide reaction is combined with 50 parts, byweight, of the alkylene oxide, i. e., the intermediate polyepoxide 3derivative may contribute somewhat'less than 2% of the totaloxyalkylated molecule. The word oxyalkylated is employed in this sensefor purpose of convenience in referring to the mono-epoxide derivativesonly.

For purpose of convenience what is said hereinafter will be divided intofive parts:

Part 1 is concerned with the non-aryl diepoxides employed withreactants;

Part 2 is concerned with suitable phenol-aldehyde resins to be employedin reaction with the diepoxides;

Part 3 is concerned with reactions involving the two preceding types ofmaterials and examples obtained by such reaction. Generally speaking,this involves nothing more than a reaction between two moles of apreviously prepared phenol-aldehyde resin as described and one mole of aspecified diglycidyl ether so as to yield a new and larger resinmolecule;

Part 4 is concerned with the oxyalkylation of the previously describedresultant or cogeneric mixture which, for sake of simplicity, may bereferred to as a diepoxide derived dimer. Such language is merely anapproximation of its structure. Oxyalkylation is more convenientlyemployed in the text to indicate the use of the previously indicatedmonoepoxides;

Part 5 is concerned with the resolution of petroleum emulsionsof thewater-in-oil type by means of the previously described chemicalcompounds or reaction products.

PART 1 Reference is made to previous patents as illustrated in themanufacture of the non-aryl diepoxides employed as reactants in theinstant invention. More specifically, those patents are the following:Italian Patent 400,973, dated August 4, 1941; British Patent 518,057,dated December 10, 1938; U. S. Patent 2,070,990, dated February 16, 1937to Groll et al.; and U. S. Patent 2,581,464, dated January 8, 1952 toZech. The simplest diepoxide is probably the one derived from1,3-butadiene or isoprene. Such derivatives are obtained by the use ofperoxides or by other suitable means and the diglycidyl ethers may beindicated thus In some instances the compounds are essentiallyderivatives of etherized epichlorohydrin or methyl epichlorohydrin.Needless to say, such compounds can be derived from glycerolmonochlorohydrin by etherization prior to ring closure. An example isillustrated in the previously mentioned Italian Patent 400,973.

Another type of diepoxide is diisobutenyl dioxide as described inaforementioned U. S. Patent 2,070,990,

7 dated February 16, 1937 to Groll, and is of the following formula Thediepoxides previously described may be indicated by the followingformula in which R represents a hydrogen atom or methyl radical and R"representsthe divalent radical uniting the two terminal epoxide groups,and .n' .is the numeral .0 or 1. As previously pointed out in the caseof the butadiene derivative, n is .0. In the case of diisobutenyldioxide R" is CH2CH2 and n is .1. In another example previously referredto R" is CHzOCI-Iz and n is 1.

However, for practical" purposes the only diepoxide available inquantities other than laboratory quantities is a derivative of glycerolor epichlorohydrin. This particular diepoxide is obtained from acyclicdiglycerol and epichlorohydrin or equivalent thereof in that theepichlorohydrin itself may supply the glycerol or diglycerol radical inaddition to the epoxy rings. As has been previously suggested, insteadof starting with glycerol or a glycerol derivative, one could start withany one of a number of glycols or polyglycols and it is more convenientto include as part of the terminal oxirane ring radical the oxygen atomthat was derived from epichlorohydrin or, as might be the case, methylepichlorohydrin.

So presented the formula becomes In the above formula R1 is selectedfrom groups such as the following:

It is to be noted that in the above epoxides there is a complete absenceof (a) any] radicals and, (b) radicals in which 5 or more carbon atomsare united in a single uninterrupted single group. R1 is inherentlyhydrophile in character as indicated by the fact that it is specifiedthat the precursory diol or polyol HOROH must be water soluble insubstantially all proportions, i. e., water miscible.

Stated another way, what is said previously means that a polyepoxidesuch as is derived actually or theoretically, or at least derivable,from the diol HOROH, in which the oxygen-linked hydrogen atoms werereplaced by in which R1 is C3H5(OH) it is obvious that reaction withanother mole of cpichlorohydrin with appropriate ring closure wouldproduce a triepoxide or, similarly, if R1 happened to beC3H5(OH)OC3H5(OH), one could obtain a tetraepoxide. Actually, suchprocedure generally yields triepoxides, or mixtures with higher epoxidesand perhaps in other instances mixtures in which diepoxides are alsopresent. Our preference is to use the diepoxides.

There is available commercially at least one diglycidyl ether free fromaryl groups and also free from any radical having 5 or more carbon atomsin an uninterrupted chain. This particular .diglycidy'l ether isobtained by the use of epichlorohydrin in such a manner thatapproximately four rnoles of .epichlorohydrin yield one mole of the diglycidyl ether or, stated another way, it can be considered as beingformed from one mole of acyclic diglycerol and two moles ofepichlorohydrin so as to give the appropriate diepoxide. The molecularweight is approximately 370 and the number of epoxide groups permolecule are approximately two. For this reason, in the first of aseries of subsequent examples this particular diglycidyl ether is used,although obviously any of the other pre viously described would be justas suitable. For convenience, this diepoxide will be referred to asdiglycidyi ether A, illustrated by a prior formula.

Using laboratory procedure we have reacted diethylene glycol withepichlorohydrin and subsequently with alkali so as to produce a productwhich, on examination, corresponded approximately to the followingcompound The molecular Weight of the product was assumed to be 230 andthe product was available in laboratory quantitles only. For thisreason, the subsequent table referring to the use of this particulardiepoxide, which will be referred to as diglycidyl ether B, is in gramsinstead of pounds.

Probably the simplest terminology for these polyepoxides, andparticularly diepoxides, to differentiate from comparable aryl compoundsis the terminology epoxyalkanes and, more particularly, polyepoxyalkanesor diepoxyalkanes. The difficulty is that the majority of thesecompounds represent types inwhich a carbon atom chain is interrupted byan oxygen atom and, thus, they are not strictly alkane derivatives.Furthermore, they may be hydroxylated or represent a heterocyclic ring.The principal class properly may be referred to aspolyepoxypolyglycerols, or diepoxypolyglycerols.

Other examples of diepoxides involving a heterocyclic ring having, forexample, 3 carbon atoms and 2 oxygen atoms, are obtainable by theconventional reaction of combining erythritol with a carbonyl compound,such as formaldehyde or acetone, so as to form the 5-membered ring,followed by conversion of the terminal hydroxyl groups into epoxyradicals.

PART 2 This part is concerned with the preparation of phenolaldehyderesins of the kind described in detail in U. S. Patent No. 2,499,370,dated March 7, 1950, to De Groote and Keiser, with the followingqualifications; said aforementioned patent is limited to resins obtainedfrom difunctional phenols having 4 to 12 carbon atoms in the substituenthydrocarbon radical. For the present purpose the substituent may have asmany as 18 carbon atoms, as in the case of resins prepared fromtetradecylphenol, substantially para-tetradecylphenol, commerciallyavailable. Similarly, resins can be prepared from hexadecylphenol oroctadecylphenol. This feature will be referred to subsequently.

In addition to U. S. Patent No. 2,499,370, reference is made also to thefollowing U. S. patents: Numbers 2,499,365, 2,499,366 and 2,499,367, alldated March 7, 1950, to De Groote and Keiser. These patents, along withthe other two previously mentioned patents, describe phenolic resins ofthe kind herein employed as initial materials.

For practical purposes, the resins having 4 to 12 carbon atoms are mostsatisfactory, with the additional C14 carbon atom also being verysatisfactory. The increased cost of the C16 and C13 carbon atom phenolrenders these raw materials of less importance, at least at the presenttime.

Patent 2,499,370 describes in detail methods of preparing resins usefulas intermediates for preparing the products of the present application,and reference is made to that patent for such detailed description andto examples 1a through 103a of that patent for examples of suitableresins.

As previously noted, the hydrocarbon substituent in the phenol may haveas many as 18 carbon atoms, as illustrated by tetradecylphenol,hexadecylphenol and octadecylphenol, reference in each instance being tothe difunctional phenol, such as the orthoor para-substituted phenol ora mixture of the same. Such resins are described also in issued patents,for instance, U. S. Patent No. 2,499,365, dated March 7, 1950, to DeGroote and Keiser, such as Example 71a.

. It is sometimes desirable to present the resins herein employed in anover-simplified form which has appeared from time to time in theliterature, and particularly in the patent literature; for instance, ithas been stated that the composition is approximated in an idealizedform by the formula R R n R In the above formula n represents a smallwhole number carrying from 1 to 6, 7 or 8, or more, up to probably 10 or12 units, particularly when the resin is subiected to heating under avacuum as described in the literature. A limited sub-genus is in theinstance of low molecular weight polymers where the total number ofphenolic nuclei carries from 3 to 6, i. e., it varies from 1 to 4; Rrepresents an aliphatic hydrocarbon substituent, generally an alkylradical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl,decyl or dodecyl radical. Where the divalent bridge radical is shown asbeing derived from formaldehyde it may, of course, be derived from anyother reactive aldehyde having 8 carbon atoms or less.

In the above formula the aldehyde employed in the resin manufacture isformaldehyde. Actually some other aldehyde such as acetaldehyde,propionaldehyde, or butylraldehyde may be used. The resin unit can beexin which R' is the divalent radical obtained from the particularaldehyde employed to form the resin.

As previously stated, the preparation of resins, the kind hereinemployed as reactants, is well known. See U. S. Patent No. 2,499,368,dated March 7, 1950, to De'Groote and Keiser. Resins can be made usingan acid catalyst or basic catalyst or a catalyst showing neither acidnor basic properties in the ordinary sense or without any catalyst atall. It is preferable that the resins employed be substantially neutral.In other words, if prepared by using a strong acid as a catalyst, suchstrong acid should be neutralized. Similarly, if a strong base is usedas a catalyst it is preferable that the base be neutralized although wehave found that sometimes the reaction described proceeded more rapidlyin the presence of a small amount of a free base. The amount may be assmall as a 200th of a percent and as much as a few 10th of a percent.Sometimes moderate increase in caustic soda and caustic potash may beused. However, the most desirable procedure in practically every case isto have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one havingjust 3 units, or just 4 units, or just 5 units, or just 6 units, etc. Itis usually a mixture; for instance, one approximating 4 phenolic nucleiwill have some trimer and pentamer present. Thus, the molecular weightmay be such that it corresponds to a fractional value for n as, forexample, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for usingother than those which are lowest in price and most readily availablecommercially. For purpose of convenience suitable resins arecharacterized in the following table:

TABLE I Mo]. wt. Ex- R of resin ample R Position derived 1?. moleculenumber of R from (based on n+2) Phenyl Para. Formal- 3. 5 992. 5 dehyde.Tertiary butyl do 3. 5 882. a Secondary butyL 3. 5 882. 5 Cyclohexyl r3. 5 1, 025. 5 Tertiary amyl 3. 5 959. :1 Mixed secondary 3 5 805. 5

and tertiary amyl.

3. 5 805. 5 3. 5 I, 036. 5 3. 5 1, 190. 5 3. 5 l, 207. 5 as 1, 34.1.. 5yl. 3. 5 l, 498. 5 Tertiary buty] 3. 5 945. 5

Tertiar am I 3 5 1 022. 5 Non ijnninflu a s 1: 330. 5 Tertiary butyl 6 51, 071. 5

'Icrtiar am 1 3. 5 1, 148. 5 onylfm fl 3. 5 l, 456. 5 Tertiary butyL 3.5 l, 008. 5

Tertiary amyl '3. 5 1, 085. 5 N011 3.5 1,393.5 Tertiary bntyL v 4. 2996. 6

Tertiary arnyl 4. 2 1, 083. 4 Nonyl 4. 2 l, 430. G Tertiary butyL 4. 81, 094. 4 Tertiary amyL. 4. 8 1,189.6 N onyl 4. 8 1, 570. 4

c ex l PART 3 subsequent oxyalkylation procedure which involves amono-epoxide only. Since the polyepoxide is non-volatile as compared,for example, to ethylene oxide, the reaction is comparatively simple. Onthe other hand, purely as a matter of convenience, one generally wouldconduct both class of reactions in the same equipment. In other words,the two moles of phenol-aldehyde resin would be reacted with apolyepoxide and then subsequently with a mono-epoxide. In any event, thepolyepoxide reaction can be conducted in an ordinary reaction vessel,such as the usual glass laboratory equipment. This is particularly true.of the kind used for resin manufacture as described in a number ofpatents, a for example, previously mentioned U. S. Patent No. 2,499,365.One can use a variety of catalysts in connection with the piolyep'oxideof the same class employed with mono-epoxi-de. In fact, the reactionwill go at an extremely slow rate without any catalyst at all. The usualcatalysts include alkaline materials such as caustic soda, causticpotash, sodium methylate, etc. Other catalysts may be .acidic in natureand are of the kind characterized .by iron and tin chlorides.Furthermore, insoluble catalysts such as clays or specially preparedmineral catalysts have been used. For practical purposes it is best touse a catalyst which can remain in the reaction mass and will continueto serve as a catalyst in connection with the oxyalkylation employingthe mono-epoxide. For this reason we have preferred sodium methylate :asa catalyst. The amount generally employed is 1%, 2%, or 3% of thesealkaline catalysts.

Actually, the reactions of polyepoxides with various resin materialshave been thoroughly described in the literature and the procedure is,for all purposes, the same as with glycide which is described in detailin the next succeeding part, to wit, Part 4.

The use of an excessive amount of catalyst may produce side reactions asin the case of lycide. For the sake of simplicitythe procedure will beillustrated by examples but particular reference is made again to thefurther discussion of oxyalkyllation. reactions and procedures in Part4.

it goes without saying that the reaction can take place in an inertsolvent, i. ,c., one that is not oxyalkylationsusceptible. Generallyspeaking, this is most conveniently an aromatic solvent such as xyleneor a higher boiling coal tar solvent, or else a similar high boilingaromatic solvent obtained from petroleum. One can employ an oxygenatedsolvent such as the diethylether of ethylene glycol, or the diethyletherof propylene glycol, or similar others, either alone or in combinationwith a hydrocarbon solvent. The solvent so selected should be one which,of course, is suitable in the oxyalkylation step involving themono-epoxides described subsequently. The solvent selected may depend onthe ability to remove it by subsequent distillation if required.

Example 1 b The phenol-formaldehyde resin employed was the onepreviously identified as 38a, having a molecular weight of approximately700; the amount employed was 1408 grams. The resin was finely powderedand 1,000 grams of xylene added. The mixture was heated to approximatelyC. and stirred until the solution was complete. 26 grams of sodiummethylate were then added and stirring con tinued until completesolution or distribution was obtained. The mixture was heated to C. andleft at this temperature while 370 grams of the diepoxide, previouslyidentified as Polyepoxide A, were added. It was added in solution formand mixed with 500 grams of solvent. The solvent used was an 80-20mixture of Xylene and diethylether of ethyleneglycol. This solution wasadded dropwise. Just before the addition of the diepoxide thetemperature was raised to somewhat above 100 C.near C. The time requiredto add the diepoxide was approximately 2 hours. The temperature roseduring this period to approximately C. The product was then allowed toreflux at this approximate temperature for the next 2 /2 hours. Duringthis period there was a modest loss of xylene and the temperature roseslightly to about 130 C. Heating was then allowed to proceed for about 8hours longer and part of the xylene was removed by means of aconventional phase-separating trap so that at the end of the period thetemperature had risen to approximately C. Reiluxing was then continuedfurther with the removal of a bit more xylene and at the end of thisadditional period the temperature had reached approximately C. Theoverall reaction period was 17 hours. At the end or" this time there wasa slight residue equivalent to probably less than 5 cc. in the bottom ofthe reaction flask or pot and a slight amount of xylene was added,approximately 75 grams, in order to have the final reaction massrepresent about one-half reaction mass and one-half solvent. Subsequenttests in an evaporating dish, with due allowance for the glycol ether,showed there was approximately 49% solvent and 51% reaction mass.

The procedure employed, of course, is simple in light of what has beensaid previously and also in light of what is said in the next section.Various examples obtained in substantially the same manner areenumerated and described in the following tables:

TABLE II Dissolved in 80-20 806. mixture Percent- Resin Dissolvedmethyl- Poly- Polyepxylene Reaction Approx. age sol- Ex. No. Resin used,in xylene, ate epoxide oxide and ditemp. time of vent in used gramsgrams used, used used, eth range, 0. reaction, final grams grams etherof hrs. product ethylene glycol, grams 1b 1, 408 1, 000 26 A 370 500-160 17 49 2b. 1, 985 1, 000 35 A 370 500 90-155 16 50 3b 1, 765 1, 00049 A 370 500 85-155 18 51 4b- 2, 050 1, 000 28 A 370 500 85-160 22 505b- 2, 380 1, 000 38 A 370 500 95-160 19 49 6b 2, 535 1,000 27 A 370 50085-155 22 51 7b 1, 890 1, 000 23 A 370 500 100-145 18 50 8b 2, 660 1,000 25 A 370 500 85-160 17 49 2, 913 1, 000 36 A 370 500 80-145 51 2,017 1, 000 38 A 370 500 90-160 16 50 1, 272 1, 000 23 A 370 600 85-16020 50 1, 496 1, 000 32 A 370 500 100-145 18 51 1, 480 1, 000 27 A 370500 80-145 17 49 1, 210 1,000 A 370 500 85-155 20 50 1, 300 1, 000 28 A370 500 80-150 18 49 1. 110 1, 000 23 A 270 500 90-155 17 51 l, 380 1,000 28 A 370 600 85-160 22 50 1, 590 1, 000 26 A 870 500 90-160 18 50TABLE III TABLE V Probable Probable Probable mol. wt. of Amt. of Amt. ofnumber of Probable Amt. of Amt. of number of Ex. No. Resin reactionproduct, solvent, hydroxyls Ex. No. Resin mol. wt. of product, solvent,hydroxyls product g'rs. grs. per molereaction grs. grs. per moleculeproduct cule 1, 763 3, 578 1. 815 10 1, 613 3,178 1, 565 8 2, 343 4, 6652, 325 13 2, 193 4, 265 2, 072 11 2, 120 4, 320 2, 200 13 1, 970 3, 920i, 950 11 2, 406 4, 797 2, 391 13 2, 256 4,397 2, 141 11 2, 736 5, 4572. 721 13 2, 586 5, 057 2, 471 11 2, 890 5, 765 2, 875 13 2, 740 5, 3652, 625 11 2, 246 4, 477 2, 231 13 2, 006 4, 077 l, 981 11 3, 015 6, 0153, 000 13 2, 865 5, 615 2, 750 11 3, 268 6, 521 8, 253 13 3, 118 6, 1213,003 11 2, 372 4, 635 2, 263 13 2, 222 I 4, 235 2, 013 11 l, 627 3, 2391, 612 10 1, 477 2,839 1, 362 8 1, 851 3, 687 1, 836 10 1, 701 3, 287 1,586 8 1, 835 3, 655 1, 820 10 1, 685 3, 255 1, 570 8 1, 565 3, 115 550 91, 415 2, 715 1, 300 7 1, 665 3, 362 1, 697 9 1, 515 2, 962 1, 447 7 1,665 2, 915 1, 250 9 1, 515 2, 515 1, 000 7 1, 735 3, 455 1, 720 9 1, 5853,055 1, 470 7 1, 945 3, 875 1, 930 9 1, 795 3, 475 1, 680 7 TABLE IVDissolved in 50-50 Sod. mixture Percent- Resin Dissolved methyl- Poiy-Polyepxylene Reaction Approx. age sol- Ex. No. Resin used, in xylene,ate epoxide oxide and ditemp. time of vent in used grams grams used,used used, ethyl range, 0. reaction, final grams grams ether of hrs.product ethylene glycol, grams 1, 408 1, 000 27 B 230 250 90-155 18 501, 985 1, 000 32 B 2'30 250 90-160 16 49 1, 765 1, 000 B 230 250 85-15517 51 2, 050 1, 000 26 B 230 250 90-160 20 49 2, 380 1, 000 28 B 230 25085-160 19 2, 535 1,000 38 B 230 250 -145 22 51 1, 890 1, 000 27 B 230250 100-145 18 49 2, 660 1, 000 23 B 230 25 -155 17 50 2, 913 1, 000 25B 230 250 -155 19 51 2, 017 1, 000 26 B 230 250 85-160 22 49 1, 272 1,000 38 B 230 250 90-160 18 50 1, 496 1, 000 26 B 230 250 80-145 20 51 1,480 1, 000 27 B 230 250 -145 17 49 1, 210 1, 000 28 B 230 250 85-155 1950 1, 300 1, 000 25 B 230 250 80-150 20 51 1, 1, 000 28 B 230 250 80-15518 49 1, 380 1,000 23 B 230 250 85-160 17 50 1, 590 1, 000 25 B 230 25090-155 19 51 15 PART 4 In preparing oxyalkylated derivatives of productsof the kind which appear as examples in Part 3, we have found itparticularly advantageous to use laboratory equipment which permitscontinuous oxypropylation and oxyethylation. More specific referencewill be madeto treatment with glycide subsequently in the text. Theoxyethylation step is, of course, the same as the oxypropylation stepinsofar that two low-boiling liquids are handled in each instance. Theoxyalkylation step is carried out in a manner which is substantiallyconventional for the oxyalkylation of compounds having labile hydrogenatoms, and for that reason a detailed description of the procedure isomitted and the process will simply be illustrated by the followingexamples:

Example 1d The oxyalkylation-susceptible compound employed is the onepreviously designated as 141). The preparation stance, 5, or gallons,have been used and in some instances autoclaves having a capacity of 35to 50 gallons have been used. In some instances, as a matter ofconvenience, the transfer of the reaction masswas made from oneautoclave to the other.

In this particular run adjustment was made in the autoclave so as tooperate at a temperature of approximately 125-130 C. and at a pressureof 10 to 15 pounds per square inch. The time regulator was set so as toinject the ethylene oxide within approximately a half hour. The rotatingstirrers were set so as to operate at approximately 400 R. P. M. Thereaction went readily and, as a matter of fact, was completed in lessthan a half hour. Stirring was continued for about 40 minutes longer.The speed of reaction, particularly at the low pressure, undoubtedly wasdue in a large measure to excellent agitation and also to the highconcentration of the catalyst. The amount of ethylene oxide introducedwas approximately equal to the initial weight of the diepoxide-derivedcompound, i. 'e., 17.6 pounds. This represented a molal ratio of about40 pounds of ethylene oxide per mole of diepoxide derivative. Thetheoretical molecular weight at the end of the reaction wasapproximately 3,500. A comparatively small sample, less than 50 grams,was withdrawn merely for examination as far as solubility or emulsifyingpower was concerned and also for purpose of making some tests in variousoil field emulsions. The amount withdrawn was so small that nocognizance of this fact was included in the data or in subsequent datapresented in Tables VI, VII, V111, and IX. have withdrawn a substantialportion at the end of each step and continued oxyalkylation on a partialresidual sample. This was not the case in this series. Certain exampleswere duplicated, as hereinafter noted, and subjected to oxyalkylationwith a different oxide.

Example 2d This simply illustrated the further oxyalkylation of Example1d preceding. As previously stated, the oxyalklation-susccptiblecompound, to wit, 1d present at the beginning of this step, wasobviously the same as at the end of the prior stage (Example. 1b), towit, 15.65 pounds. The amount of oxide present in the initial step Ininnumerable comparative oxyalkylations we 7 Iamount. Thus, at the. endof the oxyalkylation step the oxide added was a total of 35.2 pounds andthe molal gallons. In other preparations small autoclaves, for inratioof ethylene oxide to diepoxide resin derivative was approximately to 1.The theoretical molecular weight was 5,085. Conditions as far astemperature and pressure were concerned were the same as in thepreceding period and in fact remained so during the entire series. Forthis reason, no further comment will be made in regard to eithertemperature or pressure. This applied also to the time period in thisinstance.

Example 3d The oxyalkylation proceeded in the same manner as describedin 1d and 2d. There was no added solvent and no added catalyst. Theoxide added was 17.6 pounds and the total oxide at the endof thereaction was 52.8 pounds. The molal ratio of oxide to diepoxide resinderivative was approximately to 1. The reaction time was the same aspreviously. The theoretical molecular weight was 6,845.

Example 4d The oxyalkylati-on was continued and the amount of oxideadded was 17.6 pounds. There was no addition of catalyst or solventduring the entire procedure. No further comment will be made in regardto these two items. "The molal ratio of oxide to resin derivative wasThe theoretical molecular weight at the end of the reaction period wasapproximately 8,605. The reaction time was three-fourths of an hour.

Example 5d The oxyalkylation was continued with the introduction of.another 17.6 pounds-of ethylene oxide. The molal ratio at the end of thereaction period was approximately 200 to 1 and the theoretical molecularweight about 10,365. The reaction time was one and' one-fourths hour.

Example 6d The same procedure was followed as in the preceding stepswith the result that at the end of the reaction period the ratio ofoxide to resin derivative was 240 to 1, and the theoretical molecularweight was approximately 12,125. The time required. to add the oxide wastwo hours.

Example 7d The same procedure was the same as before, the amount ofoxide added was the same as before, and the time required wasapproximately two hours. The ratio of oxide to resin derivative was 280to 1 and the theoretical molecular weight was approximately 13,885.

Example 8d This was the final oxyalkylation in this particular series.The amount of oxide added was the same as before and the total amount ofoxide in at the end of the step Was approximately 141 pounds. The molalratio of oxide to resin derivative was 320 to 1 and the theoreticalmolecular weight was approximately 15,645. The time required was alittle over two hours, to wit, two and one fourth hours.

The same procedure was described in the previous examples was employedin connection with a number of the other condensates describedpreviously. All these areasea 17 data have been presented in tabularform in a series of four tables, VI, VII, VIII, and IX.

In substantially every case a 25-gallon autoclave was employed, althoughin some instances the initial oxyethylation was started in a l5-gallonautoclave and then transferred to a 25-gallon autoclave. This isimmaterial but happened to be a matter of convenience only. The solventused in all cases was xylene. The catalyst used was finely powderedcaustic soda.

Referring now to Table VI it will be noted that cmpounds 1d through 40dwere obtained by the use of ethylene oxide, whereas 41d through 80d wereobtained by the use of propylene oxide alone.

Thus in reference to Table VI it is to be noted as' follows:

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit, thediepoxide treated resin, is indicated in the second column.

The amount of such derivative used is shown in the third column.

Assuming that ethylene oxide is employed, as happens to be the case inExample 1d through 40d, the amount of oxide present in the oxyalkylationderivative is shown in column 4, although in the initial step since nooxide is present there is a blank.

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as acatalyst, and the 7th column shows the amount of solvent xyleneemployed.

The 8th column states the amount of alkylene oxide derivative present inthe reaction mass at the end of the period.

As pointed as previously, in this particular series the amount ofreaction mass withdrawn for examination was so small that it was ignoredand for this reason the resin condensate in column 8 coincides with thefigure in column 3.

Column 9 shows the amount of ethylene oxide em- .ployed in the reactionmass at the end of the particular period.

Column 10 can be ignored insofar that no propylene oxide was employed.

Column 11 shows the catalyst at the end of the reaction period.

Column 12 shows the amount of solvent at the end of the reaction period.I

Column 13 shows the molal ratio of ethylene oxide to derivative.

Column 14 can be ignored for the reason that no propylene oxide wasemployed.

Referring now to Table VI. It is to be noted that the first columnrefers to Examples 1d, 2d, 3d, etc.

The second column gives the maximum temperature employed during theoxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amountof the compound, including the solvent present, with several volumes ofwater, xylene and kerosene. It sometimes happens that although xylene incomparatively small amounts will dissolve in the concentrated material,when the concentrated material in turn is diluted with xylene separationtakes place.

TABLE VI Reference is now made to Table VII. It is to be noted thatthese compounds were designated by e numbers; that is, 1e, 2e, etc.,through and including 326. They are derived in turn from compounds of dseries, to wit, 35d, 39d, 75d, and 79d. These compounds involve the useof both ethylene oxide and propylene oxide. Since compounds ld through40d were obtained with the use of ethylene oxide, it is obvious thoseobtained from 35d and 39d involve the use of ethylene oxide andpropylene oxide afterwards. Inversely, those compounds obtained from 75aand 79d obviously were obtained from a previously prepared compoundwhere propylene oxide was used first. In the series of e compounds, 1ethrough and including 32e, it will be noted that it required aduplication of four previously prepared compounds, to wit, 35d, 39d, 75dand 79d.

It is to be noted that reference to the catalyst in Table VIII refers tothe total catalyst, i. e., the, catalyst present from the firstoxyalkylation step plus added catalyst, if any. The same is true inregard to the solvent. Reference to the solvent refers to the totalsolvent present, i. e., giat from the first oxyalkylation step plusadded solvent,

any.

It will be noted also that under the molal ratio the values of bothoxides to the resin condensate are included.

The data given in regard to the operating conditions is substantiallythe same as before and appears in Table IX.

The products resulting from these procedures may contain modest amounts,or have small amounts, of the solvents as indicated by the figures inthe tables. If desired the solvent may be removed by distillation, andparticularly vacuum distillation. Such distillation also may removetraces or small amounts of uncombined oxide, if present and volatileunder the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide incombination one need not first use one oxide and then the other, but onecan mix the two oxides and thus obtain what may be termed an indifferentoxyalkylation, i. e., no attempt to selectively add one and then theother, or any other variant.

Needless to say, one could start with ethylene oxide and then usepropylene oxide, and then go back to ethylene oxide, or, inversely,start with propylene oxide, then use ethylene oxide, and then go back topropylene oxide, or, one could use a combination in which butylene oxideis used along with either one of the two oxides just mentioned, or acombination of both of them.

The resins which are employed as raw materials vary from fairly highmelting resins to resins melting near the boiling point of water, toother products whose melting points are only moderately above ordinaryroom temperature. Such resins vary in color from almost waterwhite toproducts which are dark amber or reddish amber in appearance. In someinstances they are tacky solids, or even liquids at ordinary roomtemperatures. After treatment with diepoxides of the kind hereinemployed the resultant product is usually at least as dark, perhapsdarker, than the initial resin. The solvent can be re moved readily bydistillation, particularly vacuum distillation. The product obtainedafter treatment with the described diepoxide is apt to be somewhatsofter and more liquid than the original material. In some instances atackiness develops which is suggestive of cross-linking in some obscuremanner.

When products of the kind previously described are intended forsubsequent reaction, such as oxyalkylation, the solvent and catalyst maybe permitted to remain for ultimate use.

Oxyalkylation, particularly exhaustive oxyalkylation, tends to do anumber of things such as reduce the color, make the product less viscousand may'even render a thin liquid, and may reduce the amount ofalkalinity present.

In any event whether the solvent is to be removed, or the productbleached at either stage, is simply a matter in the usual y suitable-Mo1al ratio Ethyl. *Propl.

oxide to oxy to oxyalkyl. suseept. suscept.

cmpd.

. 000.00000555-O5555000000000000000000000 .000000 .0555555555557777777733333333222222225.55.55m 555555m 5777 .or else thefinalproduct or Solvent, lbs.

further bleached Catalyst, Ib s.

6666666 OO000000 055555553333333388 88 88666666665555 5555555555555555555 8888 5.0555 %8a 88888899909999888888B877%77H775 555555888uw8 89999 .9983 3 877777777 l1.11111122222222111 111111 1 1 1 .11 112222222211L11 LLJ LLLVLLP HL Composition at end Prop]. oxide, .5-

Ethl. oxide,

0855062 5284199999 Soon 52085308765421 5555 35.55 0 00055555. 555-Mu55kv 5555-I 55 55 55555550 00 00 05555555555555555 6666656pmflfwwwwnm $4444ka A433833103366%66%66M666B6569%%99 %g 9 44444 4 44Qv33333336 holdlhccolor eta an intermediate product can be manner using earth, bleachingchars, or thelike. VUlt mately the solvent could be removedlin an TABLEVI Solvent,

inate lbs.

Propl. Oata- 1' oxide Jyst .06 0000 0 0000000 0000 39 vOOAUOMO 3692581"AQOZFDWMW 7 3 39 .9876543 0 01112 .742 4 22.581470 @600 2 ilnuxuwsom 1H 1112 11 Composition before Ethl. q'

iminate coloror solvent.

o-s m 5.

cmpd., om ex.No.

be use employed f therca of the intended ultima tion of petroleumemulsions there is no need to e! any alkalinity and no need to e1 If theproduct is to be employed in the manufacture of varnish resins theprocedure should be conducted so as to 5 manner by distillation,including vacuum distillation.

Ex. No.

' Oxyalkylation-susceptible.

TABLE VII Composition before Composition at end Molal ratio 7 Molec. Ex.No. wt.

-8 0-8 Ethl. Propl. Cata- 501- 0-8 Ethl. Propl. Cata- So1- Ethyl. Propl.based cmpd., empd., oxide, oxide, lyst, vent, 0mpd., oxide, oxide, lyst,vent, oxide oxide on theex. N 0. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs.lbs. lbs. to oxyto oxyoretlcal elkyl. alkyl. value 11 mnf 11 0mg cmpd.cmpd.

15. 65 26. 40 0. 78 15. 50 15. 65 26. 40 7. 83 O. 78 15. 50 60 13. 4,988 15. 65 26. 40 7. 83 78 15. 50 15. 65 26. 40 15. 66 78 15. 50 60 27.0 5, 771 15. 65 26.40 15. 66 78 15. 50 15. 65 26. 40 23. 49 78 15. 50 6040. 5 6, 554 15. 65 26. 4O 23. 49 78 15. 5O 15. 65 26. 40 31. 32 78 15.50 60 54 01 7, 337 15. 65 26. 40 31. 32 78 15. 50 15. 65 26. 40 39. 7815. 50 60 67. 5 8, 120 15. 65 26. 40 39. 15 78 15. 50 15. 65 26. 40 46.98 78 15. 50 60 81. 01 8, 903 15. 65 26. 40 46. 98 78 15. 50 15. 65 26.40 54. 61 78 15. 50 6O 94. 5 9, 686 15. 65 26. 40 54. 81 78 15. 50 15.65 26. 40 62. 64 78 15. 5O 60 108. 0 10, 469 15. 65 61. 60 1. 56 15. 5015. 65 61. 60 7. 83 1. 56 15. 50 140 13. 5 508 15. 65 61. 60 7. 83 1. 5615. 50 15. 65 61. 60 15. 66 1. 56 15. 50 140 27. 0 291 15. 65 61. 60 15.66 1. 56 15. 50 15. 65 61. 60 31. 32 Y 1. 56 15. 50 140 54. 0 10, 85715. 65 61. 60 31.32 1. 56 15. 50 15. 65 61. 60 39. 15 1. 56' 15. 50 14067. 5 11, 640 15. 65 61. 60 39. 15 1. 56 15. 50 15. 65 61. 60 46. 98 1.56 15. 50 140 81.0 12, 423 15. 65 61. 60 46. 98 1. 56 15. 50 15. 65 61.60 78. 1. 56 15. 50 140 135.0 15, 555 15. 65 61. 60 78. 80 1. 56 15. 5015. 65 61. 60 93. 96 1. 56 15. 50 140 162.0 17, 121 15. 65 61. 60 93.96 1. 56 15. 50 15. 65 61. 60 109. 62 1. 56 15. 50 140 189. 0 18, 68715. 65 23. 49 1. 56 15. 50 15. 65 8. 80 23. 49 1. 56 15. 50 20 40. 5 4,795 15. 65 8. 80 23. 49 1. 56 15. 50 15. 65 17. 60 23. 49 1. 56 15. 5040. 5 5, 675 15. 65 17. 60 23. 49 1. 56 15. 15. 65 26. 40 23. 49 1. 5615. 50 40. 5 6, 555 15. 26. 40 23. 49 1. 56 15. 50 15. 65 35. 20 23.49 1. 56 15. 50 40. 5 7, 435 15. 65 35. 20 23. 49 1. 56 15. 50 15. 6544. 00 23. 49 1.56 15. 50 100 40. 5 8, 315 15. 65 44.00 23. 49 1. 56 15.50 15. 65 52. 80 23. 49 1. 56 15.50 40. 5 9, 195 15. 65 52. 80 23. 49 1.56 15. 50 15. 65 61. 60 23. 49 1. 56 15. 50 40. 5 10, 075 15. 65 61. 6023. 49 1. 56 15.50 15. 65 70. 40 23. 49 1. 56 15. 50 40. 5 10, 955 15.65 54. 81 1.56 15. 50 15. 65 8. 80 54. 81 1. 56 15.50 20 94. 5 7, 92615. 65 8. 80 54. 81 1. 56 15. 50 15. 65 17. 6O 54. 81 1. 56 15.50 40 94.5 8, 806 15. 65 17. 60 54. 81 1. 56 15.50 15. 65 26. 40 54. 81 1. 56 15.50 60 94. 5 9, 686 15. 65 26. 40 54. 81 1. 56 15. 50 15.65 35. 20 54.81 1. 56 15.50 80 94. 5 10, 566 15. 65 35. 20 54. 81 1. 56 15.50 15. 6544.00 54. 81 1. 56 15. 50 100 94. 5 11, 446 15. 65 44. 00 54.81 1. 5615. 50 15. 65 61. 60 54. 81 1. 56 15. 50 140 94. 5 13, 206 30e 15. 6561. 60 54. 81 1. 56 15. 50 15. 65 70. 40 54. 81 1. 56 15. 50 160 94. 514, 086 31c.... 15. 65 70. 40 54.81 1. 56 15. 50 15. 65 88. 60 54. 81 1.56 15. 50 200 94. 5 15, 846

TABLE VIII Max. Max. Solubility Ex. temp., pres... Time, No. 0. p. s.1.hrs.

Water Xylene Kerosene 10-15 M Insoluble Soluble Insoluble. 10-15 h d Do.10-15 M S D0. 10-15 D0. 10-15 M D0. 10-15 2 D0. 10-15 D0. 10-15 D0.10-15 Do. 10-15 D0. 1015 D0. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 D0.10-15 DO. 10-15 D0. 10-15 D0. 1015 Do. 10-15 D0. 10-15 DO. 10-15 D0.10-15 DO. 10-15 Do. 10-15 D0. 10-15 Do. 10-15 DO. 10-15 D0. 10-15 Do.10-15 D0. 10-15 Do. 10-15 D0. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 D0.10-15 1 D0. 10-15 1 D0. 10-15 1 D0. 10-15 1% D0. 10-15 1% DO. 10-15 1%D0. 10-15 1% Disperslble. 10-15 2 Soluble. 10-15 2 D0. 10-15 2% D0.10-15 2% D0. 10-15 3 Do. 10-15 1% Insoluble. III-15 1% D0.

TABLE VIII-Continued Max. Max. Solubility Ex. tenn, pres., Time, No. p.5.1. hrs.

, Kerosene 125-130 10-15 Dispersible. 125-130 10-15 Soluble. 125-130 1.10- Do. 125-130 1 0-15 Do. 125-130 10-15 Do. 125-130 10-15 Do. 125-13010-15 Insoluble 125-130 10-15 Do. 125-130 .10-15 Soluble. 125-130 10-15Do. 125-130 10-15 Do. 125-130 ;10-15 Do. 125-130 ,10-15 D0. 125-130 ;10-15 Do. 125-130 10-15 Insoluble 125-130 10-15 Do. 125-130 ;10-15Dispersible. 125-130 10-15 Soluble. 125-130 10-15 Do. 125-130 10-15 D0.125-130 10-15 Do. 125-130 10-15 Do. 125-130 10-15 Insoluble 125-13010-15 Do. 125-130 10-15 Do. 125-130 10-15 D0. 125-130 10-15 D0. 125-13010-15 Dispersible. 125-130 10-15 Do. 125-130 10-15 Soluble.

TABLE IX Max. -Max Solubility temp., pres Time,

0. p. s. i. hrs.

Water Kerosene 125-130 10-15 Emulslfiablo. Insoluble 125-130 10-15 (10Do. 125-130 10-15 Do. 125-130 10-15 Do.- 125-130 10-15 D0. 125-130 10-15Dispersible. 125-130 10-15 Soluble. 125-130 10-15 D0. 125-130 10-16Insoluble. 125-130 10-15 Do. 125-130 10-15 D0. 125-130 10-15 Do. 125-13010-15 D0. 125-130 10-15 Do. 125-130 10-15 Do. 125-130 10-15 Soluble.125-130 10-15 Insoluble. 125-130 10-15 Do. 125-130 10-15 D01 125-13010-15 D0. 125-130 10-15 DO. 125-130 10-15 D0. 125-130 10-15 Do. 125-13010-15 Do. 125-130 10-15 Dispersible. 125-130 10-15 Insoluble. 125-13010-15 Do. 125-130 10-15 D0. 125-130 10-15 1 Do. 125-130 10-15 D0.125-130 10-15 3 Do. 125-130 10-15 3% Do.

N0rE.-In the above table, the time period in regard to 1e, 9e, 17c, anda, is the total time for both oxyalkylation stages. In respect to allothers the time period indicated is the time required to introduce thesecond alkylene oxide employed.

PART 5 Conventional demulsifying agents employed in the treatment of oilfield emulsions are used as such, or after dilution with any suitablesolvent, such as water, petroleum hydrocarbons, such as benzene,toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols,particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol,denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octylalcohol, etc., may be employed as diluents. Miscellaneous solvents suchas pine oil, carbon tetrachloride, sulfur dioxide extract obtained inthe refining of petroleum, etc., may be employed as diluents. Similarly,the material or materials employed as the deone or more of the solventscustomarily used in connection with conventional demulsifying agents.Moreover, said material or materials may be used alone or in admixturewith other suitable well-known classes .of demulsifying agents.

It is well known that conventional demulsifying agents may be used in awater-soluble form, or in an oil-soluble 'form, or in a form exhibitingboth 011- and water-solubility. Sometimes they may be used in a formwhich exhibits relatively limited oil-solubility. However, since suchreagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000,or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in dcsaltingpractice, such an apparent insolumulsifying agent of our process may beadmixed with bility in .Oil and water is not significant because saidrcagents undoubtedly have solubility within such concentrations. Thissame fact is true in regard to the material or materials employed as thedemulsifying agent of our process.

In practicing the present process, the treating or de mulsifying agentis used in the conventional way, well known to the art, described, forexample, in Patent 2,626,929, dated January 27, 1953, Part 3, andreference is made thereto for a description of conventional proceduresof demulsifying, including batch, continuous, and down-the-holedemulsification, the process essentially involving introducing a smallamount of demulsifier into a large amount of emulsion with adequateadmixture with or without the application of heat, and allowing themixture to stratify.

As noted above, the products herein described may be used not only indiluted form, but also may be used admixed with some other chemicaldemulsifier. A mixture which illustrates such combination is thefollowing:

Oxyalkylated derivative, for example, the product of Example 4e, 20%;

A cyclohexylamine salt of a polypropylated naphthalene monosulfonicacid, 24%;

An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

isopropyl alcohol,

The above proportions are all weight percents.

Having thus described our invention, what we claim as new and desire toobtain by Letters Patent, is:

1. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifierincluding synthetic hydrophile products; said synthetic hydrophileproducts being the oxyalkylation derivatives of the reaction productsobtained by condensing (A) an oxyalkylation-susceptible fusible, organicsolvent-soluble, water insoluble phenolaldehyde resin; said resin beingderived by reaction between a difunctional monohydric phenol and analdehyde having not over 8 carbon atoms and reactive toward said phenol;said resin being formed in the substantial absence of trifunctionalphenols; said phenol being of the formula in which R is a hydrocarbonradical having at least 4 and not more than 18 carbon atoms andsubstituted in the 2,4,6 position; and (B) non-aryl hydrophilepolyepoxides characterized by the fact that the precursory polyhydricalcohol, in which an oxygen-linked hydrogen atom is subsequentlyreplaced by the radical H H H --C-O-CH in the polyepoxide, iswater-soluble; said polyepoxides being free from reactive functionalgroups other than epoxy and hydroxyl groups and characterized by thefact that the divalent linkage uniting the terminal epoxide groups isfree from any radical having more than 4 uninterrupted carbon atoms in asingle chain; with the proviso that the ratio of reactant (A) toreactant (B) in the proportion of approximately 2 moles of (A) to 1 moleof (B); with the further proviso that said reactive compounds (A) and(B) be members of the class consisting of nonthermosettingsolvent-soluble liquids and low-melting solids; and with the finalproviso that the reaction product be a member of the class consisting ofacylationand oxyalkylation-susceptible solvent-soluble liquids andlow-melting solids; and said reaction between (A) and (B) beingconducted below the pyrolytic point of the re-" actants and theresultants of reaction; followed by an oxyalkylation step by means of analpha-beta alkylene monoepoxide having not more than 4 carbon atoms andselected from the class consisting of ethylene oxide, propylene oxide,butylene oxide, glycide and methyl-glycide.

2. The process of claim 1 in which the polyepoxides are diepoxides.

3. The process of claim 1 wherein the polyepoxides are diepoxidescontaining at least one ether linkage.

4. The process of claim 1 wherein the polyepoxides are diepoxidescontaining at least one ether linkage and at least one hydroxyl radical.

5. The process of claim 1 wherein the polyepoxides are diepoxidescontaining at least one ether linkage and at least one hydroxy radicalwith the added proviso that the total number of carbon atoms in thepolyepoxide be not over 20.

6. The process of claim 1 wherein the polyepoxides are diepoxidescontaining at least one ether linkage and at least one hydroxyl radicalwith the added proviso that the total number of carbon atoms in thepolyepoxide be not over 20 and free from any radical having more thanthree uninterrupted carbon atoms in a single chain.

7. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifierincluding synthetic hydrophile products; said synthetic hydrophileproducts being the oxyalkylation derivatives of the reaction productsobtained by condensing (A) an oxyalkylationsusceptible, fusible, organicsolvent-soluble, water-insolublephenol-aldehyde resin; said resin beingderived by reaction between a difunctional monohydric phenol and analdehyde having not over 8 carbon atoms and reactive toward said phenol;said resin being formed in the substantial absence of trifunctionalphenols; said phenol being of the formula in which R is a hydrocarbonradical having at least 4 and not more than 14 carbon atoms andsubstituted in the 2,4,6 position; and (B) non-aryl hydrophilehydroxylated diepoxides containing at least one ether linkage andcharacterized by the fact that the precursory polyhydric alcohol, inwhich an oxygen-linked hydrogen atom is subsequently replaced by theradical in the diepoxide, is water soluble; said hydroxylated diepoxidebeing free from reactive functional groups other than epoxy and hydroxylgroups and characterized by the fact that the divalent linkage unitingthe terminal epoxide groups is free from any radical having more than 3uninterrupted carbon atoms in a single chain; and total number of carbonatoms in said diepoxide being not over 20; with the proviso that theratio of reactant (A) to reactant (B) be in the proportion ofapproximately 2 moles of (A) to 1 mole of (B); with the further provisothat said reactive compounds (A) and (B) be members of the classconsisting of nonthermosetting solvent-soluble liquids and low-meltingsolids; and with the final proviso that the reaction product be a memberof the class consisting of acylationand oxyalkylation-susceptiblesolventsoluble liquids and low-melting solids; and said reaction between(A) and (B) being conducted below the pyrolytic point of the reactantsand the resultants of reaction; followed by an oxyalkylation step bymeans of an alphabeta alkylene monoepoxide having not more than 4 carbonatoms and selected from the class consisting of ethylone oxide,propylene oxide, butylene oxide, g'lycide and methylglycide. 1

8. The process of claim 7 wherein the aldehyde is formaldehyde.

9. The process of claim 7 wherein the aldehyde is formaldehyde and R issubstituted in the paraposition.

10. The process of claim 7 wherein the aldehyde is formaldehyde and R issubstituted in the paraposition and the initial resin contains not over6 phenolic units.

11. The process of claim 1 with the proviso that the synthetichydrophile products in an-equal weight of xylene are sufficient toproduce an emulsion when said xylene solution is shaken vigorously with1 to 3 volumes of Water.

'12. The process of claim 2 with the proviso that the synthetic'hydrophile products in an equal weight of 'xylene are suflicient toproduce an emulsion when said my lens solution is shaken vigorously withl to 3 volumes of water.

13. The process of claim 3 with the proviso that the synthetichydrophile products in an equal weight of xylene are sufficient toproduce an emulsion when said xylene solution is shaken vigorously with1 to 3 volumes of water.

14. The process of claim 4 with the proviso that the synthetichydrophile products in an equal weight of xylene are suti'icient toproduce an emulsion when said xylene solution is shaken vigorously withT1 to 3 volumes of water.

15. The process of claim 5 with the proviso that the synthetichydrophile products in an equal weight of xylene are sufiicient toproduce an emulsion when said. Xylene solution is shaken vigorously with1 to 3 volumes of water.

16. The process of claim 6 with the proviso that the synthetichydrophile products in an equal Weight of xylene are sufficient toproduce an emulsion when said Xylene solution is shaken vigorously with'1 to 3 volumes of water.

17. The process of claim 7 with the proviso that the synthetichydrophile products in an equal weight of xylene are sufficient .toproduce an emulsion when said Xylene solution is shaken vigorously withl to 3 volumes of water.

18. The process of claim 8 with the proviso that the synthetichydrophile products in an equal Weight of Xylene are sufiicient toproduce an emulsion when said xylene solution is shaken vigorously with1 to 3 volumes of water. 7

l9. The process of claim 9 with the proviso that the synthetichydrophile products in unequal weight of zylene are sufficient toproduce an emulsion when said xylene solution is shaken vigorouslywith-1 to 3 volumes of water.

28. The process of claim 10 with the proviso that the synthetichydrophile products in an equal weight of xylens are sutlicient toproduce an emulsion when said xylene solution is shaken vigorously withl to 3 volumes of Water.

References Cited in the file of this patent UNITED STATES PATENTS2,208,331 7 Olin a- July 16, 1940 2,224,359 Rosenblum Dec. 10, 19402,454,541 Becket a1. Nov. 23, 1948 2,499,365 De Groote et a1. Mar. 7,1950 2,507,910 Keiser eta l. May 16, 1950 2,568,116 De Groote et al.Sept. 18, 1951 2,602,052 De Groote July 1, 1952 2,615,853 Kirkpatrick etal. Oct. 28, 1952

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE,CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIERINCLUDING SYNTHETIC HYDROPHILE PRODUCTS; SAID SYNTHETIC HYDROPHILEPRODUCTS BEING THE OXYALKYLATION DERIVATIVES OF THE REACTION PRODUCTSOBTAINED BY CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE FUSIBLE, ORGANICSOLVENT-SOLUBLE, WATER INSOLUBLE PHENOLALDEHYDE RESIN; SAID RESIN BEINGDRIVED BY REACTION BETWEEN A DIFUNTIONAL MONOHYDRIC PHENOL AND ANALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL:SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONALPHENOLS; SAID PHENOL BEING OF THE FORMULA